US4036590A - Method and apparatus for the automatic analysis of the concentration of an individual component of a fluid in a metal-depositing bath having several components - Google Patents

Method and apparatus for the automatic analysis of the concentration of an individual component of a fluid in a metal-depositing bath having several components Download PDF

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Publication number
US4036590A
US4036590A US05/689,925 US68992576A US4036590A US 4036590 A US4036590 A US 4036590A US 68992576 A US68992576 A US 68992576A US 4036590 A US4036590 A US 4036590A
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Prior art keywords
bath
fluid
solvent
concentration
diluted
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Expired - Lifetime
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US05/689,925
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English (en)
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Johannes Helder
Hubert De Steur
Marc De Vogelaere
Wolfgang Pernegger
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Siemens AG
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Siemens AG
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/205—Metals in liquid state, e.g. molten metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/11—Automated chemical analysis

Definitions

  • This invention relates to a method and apparatus for automatic analysis of the concentration of an individual component of a fluid in a metal depositing bath.
  • a colorimetric method of analysis is commonly employed.
  • Such a method includes the use of the dyestuff "Astraviolet", 1-methyl-2-(p-diethylaminostyrene-3,3'dimethylindol) chloride (see Armeanu and Baloui, Anal. Chim. Acta, volume 44, [1969] pages 230 to 232).
  • a quantity such a 1 ml of the bath solution is highly dilued in a first step.
  • a measured fractional quantity such a 1 ml is then taken from this highly diluted quantity.
  • the Astraviolet, as well as a solvent, such as benzene is added.
  • This solution is then intensively stirred. After a rest period, the phases separate into a heavier water phase and a lighter benzene-Astraviolet-gold phase.
  • the solvent as well as the Astraviolet must be in a specific ratio within the diluted bath fluid so that a precise assessment as to the concentration of the gold contained in the solution is possible during the subsequent colorimetric measurement and interpolation with the aid of a calibration curve.
  • a different reagent such as Malachite green may be used. See the Roumanian Review of Chemistry (1968), vol. 13, pages 1617 to 1621. There, the procedure is similar to that the described above and the extraction solvent used may be ethyl ether or carbon tetrachloride.
  • An object of the invention is therefore to automate the above described method for determining the quantity of concentration of a bath component, particularly a gold component whereby the method can be repeated in short time intervals and can be carried out by use of a comparatively small analyzing device which provides a precise analysis.
  • the bath fluid is pumped to a circulating system located partially outside of the bath.
  • a sample of the fluid is then taken from this circulating system as a first step.
  • the bath fluid quantity is diluted in at least two stages.
  • a measured fractional quantity is removed from the first dilution stage and further diluted.
  • the reaction agent and solvent are added to the measured quantity of highly diluted bath fluid, and, preferably in a repeated cycle, the measuring curvette of the colorimeter is rinsed with the solvent-reagent- mixture prior to carrying out the colorimetric measurement.
  • the bath fluid is first pumped around in the circulating system for several minutes to insure that the bath fluid taken from the bath and made available for analysis corresponds to the fluid in the bath at the time of measurement. The further the bath is separated from the analyzing device the more important this method step becomes.
  • a dilution of 1:3 ⁇ 10 3 is preferable
  • a more uniform distribution of the bath fluid in the diluting agent here, water
  • water is obtained.
  • the dilution process is carried out in several stages, however, such as first taking 1 ml of the bath fluid and diluting it with 99 ml of distilled water, stirring this mixture and then again taking 1 ml and diluting with distilled water, a much more uniform distribution of the fluid in the diluting agent is obtained over a shorter treatment period and within a small area.
  • the apparatus consists of three stationary receptacles: a receiving receptacle for the bath fluid which is to be analyzed; a diluting receptacle for the fluid which is to be analyzed; and a reaction receptacle for receiving the diluted fluid with the reaction agent and the organic solvent.
  • First and second pipettes are arranged over two of the receptacles, respectively. Each pipette connects with a piston pump. The pipettes are mounted to a common automatically operable support holder.
  • the first pipette In one position of the holder, the first pipette is arranged over the receiving receptacle and the second pipette over the diluting receptacle. In an alternate position of the support holder, the first pipette is arranged over the diluting receptacle and the second pipette over the reaction receptacle. In both positions of the support holder, the mouths of the pipettes dip into the receptacles.
  • Both pipettes are connected to piston pumps through shift or change-over valves.
  • one of the pipettes When one of the pipettes is actuated by a control device through the pistons and shift valves, it moves a measured quantity of fluid from one receptacle and deposits in one of the other receptacles a quantity which has been greatly increased by the diluting agent, preferably distilled water.
  • the device functions such that the first pipette removes 0.5 ml of bath fluid from the receiving receptacle. This pipette is conveyed over the adjacent diluting receptacle by means of the support holder and discharges the quantity of bath fluid plus 10 ml of the diluting agent.
  • This diluting agent may be delivered by means of several loading and expulsion strokes of the piston pump. For example, five piston strokes provide 50 ml of diluting agent to 0.5 ml of bath fluid. Stirring devices in the receptacles thoroughly mix the fluid. After returning the support holder to its original position, the second pipette takes 0.5 ml of diluted bath fluid from the diluting receptacle and expels this quantity, in addition to 10 ml of diluting agent, into the reaction receptacle. After repeated stirring, precisely measured quantities of solvent and reaction agent are introduced into the reaction receptacle. In the case of gold baths, preferably benzene and Astraviolet are used as the solvent and reaction agent.
  • FIG. 1 illustrates the conveyance of bath fluid in an analyzer system
  • FIG. 2 illustrates the mode of operation of the analyzer of this invention
  • FIG. 3 illustrates a schematic diagram of an analyzer device such as for a gold bath.
  • a metal-depositing bath G such as a gold bath is illustrated.
  • This bath is connected via a line L1 to sampling devices A through C.
  • sampling devices A through C These devices are constructed here as overflow containers, however, they may also be constucted as flowthrough cuvettes or sampling valves and pumps.
  • the devices are connected to a storage container D via overflow lines L2 through L4.
  • a double pump P conveys bath fluid through line L1 and then through sampling devices A through C. Overflowing bath fluid goes into storage container D, and from there back to container G through drain line L5.
  • Devices A through C are each respectively assigned to an analysis section of an analyzer not illustrated here.
  • G is a gold bath
  • container A1 functions as the receiving container for the bath fluid of the gold analysis in section 1 which determines the concentration or quantity of the gold component.
  • a valve and a pump 101 are provided for the analysis section which determines cobalt content.
  • a cuvette 102 is assigned to a pH value device C. All analysis sections are connected to a control device, not illustrated here. The control device controls the supply of corrective solution to the bath.
  • the double pump P Prior to the beginning of a bath fluid analysis, the double pump P is put in operation. It is important here that pump starting occurs a sufficient length of time prior to the beginning of the analysis, such as at least 2 minutes. Preferably, the double pump is kept in constant operation. This insures that the sampling devices A through C are filled with fresh bath fluid so that the measurement relates to the actual state of the bath fluid at the time of measurement.
  • FIG. 2 shows a functional diagram of gold analyzer 1 which will serve as a basis for the method explained in detail hereafter.
  • Pipettes P1 and P2 are connected to one another by means of a traverse 2.
  • Containers A1 through A3 of the gold analyzer are well supported on a plate which is not illustrated.
  • Traverse 2 can be moved from a position I to a position II such that, in position I, pipette P1 dips into container A1, and in position II, dips into container A2. Pipette P2, in position I dips into container A2, and a position II, dips into container A3.
  • Container A1 is the receiving container A as shown in FIG. 1.
  • Container A2 is the so-called diluting container, and container A3 the reaction container.
  • the analysis operation is centrally controlled by a program device not illustrated here.
  • Bath fluid for example, 0.5 ml
  • Bath fluid is removed by means of first pipette P1 with the aid of a pneumatically operated piston pump K1 via a shift valve S1.
  • the shift valve S1 is in the position b-c.
  • Both pipettes P1 and P2, as well as all connecting lines, are filled with distilled water.
  • a quantity of bath fluid corresponding to the increase in volume of the piston pump is drawn into the pipette.
  • valve S2 The shifting of valve S2 to a filling stroke and a discharge stroke takes place automatically six times, so that the bath sample of 0.5 ml together with 60 ml of distilled water flows into the diluting receptacle A2.
  • the mixture in dilution receptacle A2 is subsequently stirred by a magnetic stirrer (FIG. 3).
  • the traverse 2 is returned to position 1 at the command of the control device.
  • valve S1 shifts to position a-b.
  • Pipette P2 is again dipped into the dilution receptacle.
  • By activating piston pump K1 a 0.5 ml diluted bath sample is removed by pipette P2, whereupon the traverse moves to position II.
  • reaction receptacle A3 An additional filling stroke and discharge stroke of piston pump K2 occurs, so than now 10 ml of water flows into reaction receptacle A3 via pipette P2.
  • reaction receptacle A3 the previously diluted bath sample together with 10 ml of water are located, and, through stirring, a second dilution takes place.
  • a measured quantity of Astraviolet solution and via line L7, a precisely measured quantity of solvent, preferably benzene, are discharged into the reaction receptacle. This misture is stirred for 5 minutes. The Astraviolet-gold cyanide-complex is thereby transferred into the benzene phase.
  • the extraction of the benzene phase is dependent upon the temperature.
  • a temperature sensor is therefor arranged on the reaction receptacle.
  • FIG. 3 A sample embodiment of an analysis device operating according to the above described method is illustrated in FIG. 3.
  • the traverse 2 positions pipettes P1 and P2 in one position over receptacles A1 and A2, and in the other position over receptacles A2 and A3.
  • the traverse 2 is connected to a support structure 7 which is joined to a movable mounting 8. If the movable mounting is swung from the position illustrated by the solid line in the direction of arrow 9 into the position illustrated by a broken line, pipettes P1 and P2 are thereby raised and transferred from the positions shown by solid lines to the positions shown by broken lines. The pipettes return to the original position in the direction of arrow 11.
  • Movable mounting 8 is connected to a servo-motor, not illustrated here, at shaft 12, the regulating and switching operations of the servo-motor taking place by the control device of the analyzer, not shown.
  • the arrangement of pipettes P1 and P2, as well as the measurement of diameter w of diluting receptacle A2, is effected such that the mouth of the pipette dips into the fluid only to a depth t of approximately 5 mm. Such a depth prevents the adhesion of sample fluid to the outer wall of the pipette and avoids the transfer of sample fluid to the adjacent receptacle. Therefore, erroneous measurements are prevented.
  • piston pumps K3 to K5 are connected with lines L6 through L8, respectively. These pumps are constructed in the same manner as pumps K1 or K2.
  • pump K4 is connected to a reaction agent storage container (not shown) via a line L6' which, in the case of a gold bath analyzer, corresponds to a receptacle containing the Astraviolet.
  • Shift valve S5 in one position, connects the reaction agent storage container to the interior of piston K4 such that, during the intake stroke of the piston, the piston interior is filled with Astraviolet solution. If the valve is decanted by means of the control device, the piston interior is then connected to the reaction container A3 via line L6.
  • Piston K3 is also constructed in corresponding fashion and has a line L7' connected to the storage receptacle containing the solvent.
  • a first rinsing stroke takes place. Measuring fluid is thereby drawn up into the measuring cuvette and then, during the return stroke of the piston, is expelled by piston K5 to rinse the cuvette. After a short time, another rinsing stroke as described above takes place. After repeated separation of the phases in the reaction container A3, a measuring stroke of the piston K5 finally occurs. This method step serves to rinse out the cuvette windows.
  • Colorimeter 13 is connected to a regulating device for measured quantities in known fashion. This device controls the supply of corrective fluid to bath G via line L9 (FIG. 1).
  • Line L9 has a control valve V. It is connected to a receptacle E containing a corrective solution. This receptacle is under constant gas pressure. The opening of valve V is controlled by the colorimeter 13, via the regulating device.
  • Containers A1 through A3 are stabilized on a platform 14.
  • the mutual spacing between the container center axes A1' through A3' corresponds to the spacing between pipette P1 and P3.
  • Motors for magnetic stirring are arranged beneath containers A2 and A3 which cause the stirring blades 15 mounted in the receptacles to rotate. Stirring arrangements of this type are known and are not the subject of this invention.
  • control valves and drains 16 and 16' of both containers are opened so that the fluids contained therein are drained off by means of lines L10 and channelled to container F.
  • these containers are rinsed out with acetone.
  • the process of rinsing takes place via line L11 which is connected to the piston K6.
  • the shift valve S6, in turn, is connected to an acetone storage container via line 11'.

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  • Physics & Mathematics (AREA)
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  • Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
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US05/689,925 1975-06-03 1976-05-25 Method and apparatus for the automatic analysis of the concentration of an individual component of a fluid in a metal-depositing bath having several components Expired - Lifetime US4036590A (en)

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Application Number Priority Date Filing Date Title
DT2524611 1975-06-03
DE19752524611 DE2524611B2 (de) 1975-06-03 1975-06-03 Vorrichtung zum selbsttaetigen ermitteln der groesse einer spezifischen komponente einer mehrere stoffkomponenten aufweisenden probefluessigkeit eines metallabscheidenden bades

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US (1) US4036590A (de)
JP (1) JPS51150391A (de)
BE (1) BE842410A (de)
CA (1) CA1063003A (de)
DE (1) DE2524611B2 (de)
FR (1) FR2313671A1 (de)
GB (1) GB1541730A (de)
IT (1) IT1081072B (de)
NL (1) NL7604811A (de)
SE (1) SE7605916L (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859605A (en) * 1986-12-16 1989-08-22 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4894345A (en) * 1986-12-16 1990-01-16 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4900683A (en) * 1986-12-16 1990-02-13 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4925628A (en) * 1986-12-16 1990-05-15 Ciba-Geigy Corporation Sample preparation chamber with mixer/grinder and sample aliquot isolation
US4980130A (en) * 1986-12-16 1990-12-25 Ciba-Geigy Corporation System for preparation of samples for analysis
US20030049850A1 (en) * 2001-09-12 2003-03-13 Golden Josh H. Enhanced detection of metal plating additives
US7531134B1 (en) * 2002-03-08 2009-05-12 Metara, Inc. Method and apparatus for automated analysis and characterization of chemical constituents of process solutions
US20150112629A1 (en) * 2011-04-08 2015-04-23 Uniflex Company, Ltd. Validation method for automated analyzers
CN114798018A (zh) * 2022-03-09 2022-07-29 扬州大学 一种多功能微流控芯片

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111375760B (zh) * 2020-04-28 2022-06-28 中国科学院海洋研究所 一种以卡拉胶作还原剂的Au-Ag纳米核壳材料及其制备方法和应用
CN114910303A (zh) * 2022-05-24 2022-08-16 力合科技（湖南）股份有限公司 湿法冶金采样及制样系统

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192968A (en) * 1962-07-02 1965-07-06 Warner Lambert Pharmaceutical Apparatus for performing analytical procedures
US3567389A (en) * 1968-04-03 1971-03-02 Coulter Electronics Fluid transfer valve structure
US3572998A (en) * 1969-05-12 1971-03-30 Erik W Anthon Liquid sampling and pipetting apparatus
US3716338A (en) * 1968-06-14 1973-02-13 Hycel Inc Sample fluid dispensing apparatus for chemical testing apparatus
US3764268A (en) * 1971-01-12 1973-10-09 Damon Corp Constituents measuring chemical analyzer having sample processing conduit feeding aliquot processing conveyor system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3192968A (en) * 1962-07-02 1965-07-06 Warner Lambert Pharmaceutical Apparatus for performing analytical procedures
US3567389A (en) * 1968-04-03 1971-03-02 Coulter Electronics Fluid transfer valve structure
US3716338A (en) * 1968-06-14 1973-02-13 Hycel Inc Sample fluid dispensing apparatus for chemical testing apparatus
US3572998A (en) * 1969-05-12 1971-03-30 Erik W Anthon Liquid sampling and pipetting apparatus
US3764268A (en) * 1971-01-12 1973-10-09 Damon Corp Constituents measuring chemical analyzer having sample processing conduit feeding aliquot processing conveyor system

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4859605A (en) * 1986-12-16 1989-08-22 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4894345A (en) * 1986-12-16 1990-01-16 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4900683A (en) * 1986-12-16 1990-02-13 Ciba-Geigy Corporation Process for preparation of samples for analysis
US4925628A (en) * 1986-12-16 1990-05-15 Ciba-Geigy Corporation Sample preparation chamber with mixer/grinder and sample aliquot isolation
US4980130A (en) * 1986-12-16 1990-12-25 Ciba-Geigy Corporation System for preparation of samples for analysis
US20030049850A1 (en) * 2001-09-12 2003-03-13 Golden Josh H. Enhanced detection of metal plating additives
WO2003023395A1 (en) * 2001-09-12 2003-03-20 Microbar Systems, Inc. Enhanced detection of metal plating additives
US7531134B1 (en) * 2002-03-08 2009-05-12 Metara, Inc. Method and apparatus for automated analysis and characterization of chemical constituents of process solutions
US20150112629A1 (en) * 2011-04-08 2015-04-23 Uniflex Company, Ltd. Validation method for automated analyzers
US9588132B2 (en) * 2011-04-08 2017-03-07 Artel, Inc. Validation method for automated analyzers
CN114798018A (zh) * 2022-03-09 2022-07-29 扬州大学 一种多功能微流控芯片
CN114798018B (zh) * 2022-03-09 2023-05-12 扬州大学 一种多功能微流控芯片

Also Published As

Publication number Publication date
DE2524611B2 (de) 1977-07-14
GB1541730A (en) 1979-03-07
FR2313671A1 (fr) 1976-12-31
CA1063003A (en) 1979-09-25
JPS51150391A (en) 1976-12-23
DE2524611C3 (de) 1978-04-06
SE7605916L (sv) 1976-12-04
BE842410A (nl) 1976-09-16
FR2313671B1 (de) 1979-04-27
DE2524611A1 (de) 1976-12-09
NL7604811A (nl) 1976-12-07
IT1081072B (it) 1985-05-16

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